CN115678478B - Elastic single-component moisture-curing adhesive and application thereof - Google Patents
Elastic single-component moisture-curing adhesive and application thereof Download PDFInfo
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- CN115678478B CN115678478B CN202210160300.0A CN202210160300A CN115678478B CN 115678478 B CN115678478 B CN 115678478B CN 202210160300 A CN202210160300 A CN 202210160300A CN 115678478 B CN115678478 B CN 115678478B
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- polyester polyol
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- 239000004839 Moisture curing adhesive Substances 0.000 title claims abstract description 13
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 95
- 239000012948 isocyanate Substances 0.000 claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 claims abstract description 29
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 239000000853 adhesive Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 229920000728 polyester Polymers 0.000 claims abstract description 17
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000077 silane Inorganic materials 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 isocyanate siloxane Chemical class 0.000 claims description 13
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 claims description 2
- NSPSPMKCKIPQBH-UHFFFAOYSA-K bismuth;7,7-dimethyloctanoate Chemical compound [Bi+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O NSPSPMKCKIPQBH-UHFFFAOYSA-K 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 9
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001723 curing Methods 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 16
- 239000004744 fabric Substances 0.000 description 16
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 15
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000001816 cooling Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 10
- 150000002009 diols Chemical class 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 8
- 235000011037 adipic acid Nutrition 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 8
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
- 229940117969 neopentyl glycol Drugs 0.000 description 7
- JLVWYWVLMFVCDI-UHFFFAOYSA-N diethyl benzene-1,3-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC(C(=O)OCC)=C1 JLVWYWVLMFVCDI-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 4
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 2
- ONIHPYYWNBVMID-UHFFFAOYSA-N diethyl benzene-1,4-dicarboxylate Chemical compound CCOC(=O)C1=CC=C(C(=O)OCC)C=C1 ONIHPYYWNBVMID-UHFFFAOYSA-N 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- GTZOYNFRVVHLDZ-UHFFFAOYSA-N dodecane-1,1-diol Chemical compound CCCCCCCCCCCC(O)O GTZOYNFRVVHLDZ-UHFFFAOYSA-N 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229940100573 methylpropanediol Drugs 0.000 description 2
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 2
- ZLBFMYQIKPWYBC-UHFFFAOYSA-N 2-benzofuran-1,3-dione;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C1=CC=C2C(=O)OC(=O)C2=C1 ZLBFMYQIKPWYBC-UHFFFAOYSA-N 0.000 description 1
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to a curing adhesive (IPC (International patent Classification) No. C09J 167/00), in particular to an elastic single-component moisture curing adhesive and application thereof. The raw materials at least comprise the following components in parts by weight: 45-100 parts of polyester polyol, 0-5 parts of auxiliary agent, 5-30 parts of isocyanate, 5-50 parts of solvent, 0.01-0.2 part of catalyst and 0-15 parts of silane modified polyester prepolymer. The invention fully utilizes the advantages of each polyester polyol, and effectively improves the elasticity, strength, adhesive force, low temperature resistance and high temperature resistance of the adhesive. Meanwhile, the invention adopts trifunctional polyether or trimethylolpropane, so that the polymer can form a better cross-linked network, the rebound resilience of the product is effectively improved, and the invention is used on reflective materials, thereby effectively improving the washing resistance and wear resistance of luminescent materials.
Description
Technical Field
The invention relates to a curing adhesive (IPC (International patent Classification) No. C09J 167/00), in particular to an elastic single-component moisture curing adhesive and application thereof.
Background
The reflective material can reflect light of the light source back to the original place in a dim place due to the reflective property of the reflective material, and gives warning to people, so that the reflective material is favored in the fields of transportation, warning clothing and the like. Most researchers have focused on the reflection intensity and reflection principle of the reflection material, and in the effort of years we can prepare the reflection material with high reflection intensity. However, there is little interest in adhesives for retroreflective applications, so there is room for development in the research of adhesives for retroreflective materials. The adhesive is an extremely important link in the manufacture of the reflective material. The quality of the adhesive performance directly reflects the durability of the reflective material and the range of application domains.
Patent application CN201410373935.4 discloses an adhesive composition which can be used for luminescent materials, in this application, the bonding strength of glass beads on a substrate is ensured, and meanwhile, the use amount of a binder is reduced, but the inorganic filler added in the application document influences the elasticity of the adhesive and the weather resistance of the adhesive.
Therefore, the invention fully utilizes the advantages of each polyester polyol, and effectively improves the elasticity, strength, adhesive force, low temperature resistance and high temperature resistance of the adhesive. Meanwhile, the invention adopts trifunctional polyether or trimethylolpropane, so that the polymer can form a better cross-linked network, the rebound resilience of the product is effectively improved, and the invention is used on reflective materials, thereby effectively improving the washing resistance and wear resistance of luminescent materials.
Disclosure of Invention
In order to solve the above problems, the first aspect of the present invention provides an elastic single-component moisture-curable adhesive, which comprises the following raw materials in parts by weight: 45-100 parts of mixed polyester polyol, 0-5 parts of polyfunctional polyether, 5-30 parts of isocyanate, 5-50 parts of solvent, 0.01-0.2 part of catalyst and 0-15 parts of auxiliary agent;
As a preferable scheme, the elastic single-component moisture-curing adhesive comprises the following raw materials in parts by weight: 60 to 80 parts of mixed polyester polyol, 2 to 3 parts of polyfunctional polyether, 10 to 20 parts of isocyanate, 15 to 30 parts of solvent, 0.05 to 0.1 part of catalyst and 5 to 7 parts of auxiliary agent.
As a preferred embodiment, the mixed polyester polyol comprises 30-50 parts of semi-crystalline phthalic anhydride-containing polyester polyol, 5-20 parts of low crystallinity polyester polyol, and 10-30 parts of high molecular weight polyester polyol.
As a preferred embodiment, the semi-crystalline phthalic anhydride-containing polyester polyol, low crystallinity polyester polyol, high molecular weight polyester polyol is present in a weight ratio of (35 to 45): (8-12): (15-20).
As a preferred embodiment, the semi-crystalline phthalic anhydride-containing polyester polyol is an aromatic dicarboxylic acid or anhydride, and the diol is a polycondensate obtained by reacting a dicarboxylic acid with a diol.
As a preferred embodiment, the aromatic dicarboxylic acid is one or more of phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, and diethyl terephthalate.
As a preferred embodiment, the glycol is one or more of methylpropanediol, neopentylglycol, 3-methyl-1, 5-pentanediol, trimethylpentanediol, ethylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, diethylene glycol.
As a preferred embodiment, the dibasic acid is one or more of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid.
As a preferred embodiment, the semi-crystalline phthalic anhydride-containing polyester polyol is a diethylene glycol-phthalic anhydride polyester polyol. Commercially available, e.g. PDP-70 from Su Telin (Nanjing) New Material technologies Co., ltd
As a preferred embodiment, the low crystallinity polyester polyol is a polycondensate of an aliphatic dicarboxylic acid and a side group-containing diol.
As a preferred embodiment, the low crystallinity polyester polyol has a number average molecular weight of 1900 to 2100g/mol.
As a preferred embodiment, the aliphatic dicarboxylic acid is one or more of succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid.
As a preferred embodiment, the diol containing pendant groups is one or more of methylpropanediol, neopentylglycol, 3-methyl-1, 5-pentanediol, trimethylpentanediol.
As a preferred embodiment, the low crystallinity polyester polyol is one or more of succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid.
As a preferred embodiment, the high molecular weight polyester polyol is an aromatic dicarboxylic acid, a polycondensate of a long chain fatty acid and a glycol.
As a preferred embodiment, the high molecular weight polyester polyol is a polycondensate of diethyl isophthalate, adipic acid, neopentyl glycol.
As a preferred embodiment, the high molecular weight polyester polyol has a molecular weight of 3900 to 4100g/mol.
As a preferred embodiment, the aromatic dicarboxylic acid is one or more of isophthalic acid, terephthalic acid, dimethyl isophthalate, diethyl isophthalate, dimethyl terephthalate, and diethyl terephthalate.
As a preferred embodiment, the long chain fatty acid is one or more of adipic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid.
As a preferred embodiment, the dihydric alcohol is one or more of methyl propylene glycol, neopentyl glycol, 3-methyl-1, 5-pentane diol, trimethyl pentane diol, ethylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, diethylene glycol.
As a preferred embodiment, the polyfunctional polyether is a trifunctional polyether.
As a preferred embodiment, the hydroxyl value of the trifunctional polyether is 920 to 980mgKOH/g.
As a preferred embodiment, the trifunctional polyether is commercially available, for example, french sepiline 3095,095.
As a preferable scheme, the weight ratio of the mixed polyester polyol to the polyfunctional polyether is (24-32): 1.
As a preferred embodiment, the isocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), carbodiimide-modified diphenylmethane diisocyanate.
As a preferred embodiment, the isocyanate is a mixture of HDI and IPDI.
As a preferable scheme, the weight ratio of the HDI to the IPDI is 1: (2-4).
As a preferable scheme, the solvent is one or more of ethyl acetate, methyl acetate, acetone, butanone and toluene.
As a preferred embodiment, the solvent is a mixture of ethyl acetate and toluene.
As a preferable scheme, the weight ratio of the ethyl acetate to the toluene is (2-3): 1.
As a preferred scheme, the catalyst is one or more of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate and composite organic bismuth zinc.
As a preferred embodiment, the catalyst is bismuth isooctanoate.
As a preferred embodiment, the auxiliary agent is a silane-modified polyester prepolymer.
As a preferred embodiment, the silane-modified polyester prepolymer is the reaction product of a low crystalline polyester polyol and an isocyanate siloxane.
As a preferred embodiment, the isocyanate siloxane is one or more of 3-isocyanatopropyl methyl dimethoxy silane, 3-isocyanatopropyl methyl diethoxy silane, 3-isocyanatopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane, and 3-isocyanatopropyl triethoxy silane.
As a preferred scheme, the preparation method of the silane modified polyester prepolymer comprises the following steps: (1) Adding low-crystallization polyester polyol into a high-order reaction kettle, heating to 110-120 ℃, vacuumizing to a vacuum degree of minus 0.09-minus 0.1MPa, dehydrating until the water content is below 500ppm, cooling to below 80 ℃, and introducing nitrogen. (2) Adding isocyanate siloxane, and reacting for more than 2 hours to obtain the silane modified polyester product.
As a preferred embodiment, the low crystalline polyester polyol, isocyanate silicone has a weight ratio of 1: (0.15-0.4).
As a preferable scheme, the weight ratio of the isocyanate and the silane modified polyester prepolymer is (2-3): 1.
The preparation method of the single-component moisture-curing adhesive comprises the following steps:
(1) Adding polyester polyol and polyfunctional polyether into a reaction kettle, heating, dehydrating, and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent (accounting for 10-30% of the weight of the component A), introducing nitrogen to perform prepolymerization reaction, adding a catalyst, and continuing the reaction to obtain a mixture B;
(3) And adding an auxiliary agent and the rest solvent into the mixture B, cooling and discharging to obtain the adhesive.
The invention fully utilizes the advantages of each polyester polyol, and ensures that the product has excellent elasticity, strength, adhesive force, low temperature resistance and high temperature resistance. Meanwhile, the invention adopts trifunctional polyether or trimethylolpropane, so that the polymer can form a better cross-linked network, and the rebound resilience of the product is effectively improved. In general, high-solid-content single-component glue is synthesized, and a glue film layer with sufficient toughness and good elasticity is formed by utilizing moisture curing reaction and is resistant to water washing.
The beneficial effects are that:
1. The invention uses semi-crystalline polyester polyol with phthalic anhydride, low crystallinity polyester polyol and high molecular weight polyester polyol with the weight ratio of (35-45): (8-12): (15-20), the primary bonding strength and the final bonding strength of the product are effectively improved, and meanwhile, the elasticity and the washing resistance of the product are also improved.
2. The invention mixes polyester polyol and the weight ratio of polyfunctional polyether is (24-32): 1, the rebound resilience of the product is effectively improved, and meanwhile, the strength of the product is also improved.
3. The weight ratio of the isocyanate and the silane modified polyester prepolymer is (2-3): 1, the bonding effect of the product on the reflective material is effectively improved, and the water resistance is improved.
4. The adhesive prepared by the invention is high-solid-content single-component glue, and forms a glue film layer with sufficient toughness and good elasticity by utilizing the curing reaction of the glue, and has excellent washing resistance.
Detailed Description
Examples
Example 1
The embodiment 1 of the invention provides an elastic single-component moisture-curing adhesive, which comprises the following raw materials in parts by weight: 70 parts of mixed polyester polyol, 2 parts of polyfunctional polyether, 15 parts of isocyanate, 20 parts of solvent, 0.08 part of catalyst and 6 parts of auxiliary agent.
The mixed polyester polyol in this example comprises 40 parts of semi-crystalline phthalic anhydride-containing polyester polyol, 10 parts of low crystallinity polyester polyol, and 17 parts of high molecular weight polyester polyol.
The semi-crystalline phthalic anhydride-containing polyester polyol in this example is an aromatic dicarboxylic acid or anhydride, and a polycondensate obtained by reacting a diol with a diacid.
Semi-crystalline phthalic anhydride-containing polyester polyols in this implementation were purchased from Su Telin (Nanj) new materials technology Co.Ltd.
The low crystallinity polyester polyol in this embodiment is a polycondensate of an aliphatic dicarboxylic acid and a pendent diol.
The number average molecular weight of the low crystallinity polyester polyol in this example was 2000g/mol.
The low-crystallinity polyester polyol is PA-56N of Nanjing hand-in-hand chemical industry Co., ltd.
The high molecular weight polyester polyol in this example is a polycondensate of diethyl isophthalate, adipic acid, neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol. The high molecular weight polyester polyol in this example is Shandong national chemical Co.
The polyfunctional polyether in this example is a trifunctional polyether, which is purchased from sepiline 3095,095, france.
The isocyanate in this example is a mixture of HDI and IPDI.
In this embodiment, the weight ratio of HDI to IPDI is 1:3.
The solvent in this example was ethyl acetate, a mixture of toluene.
In this example, the weight ratio of ethyl acetate to toluene is 2:1.
The catalyst in this example was bismuth isooctanoate purchased from Jinan Bing chemical Co.
The adjuvant in this example is a silane modified polyester prepolymer which is the reaction product of a low crystalline polyester polyol and an isocyanate siloxane.
The weight ratio of the low crystalline polyester polyol to isocyanate silicone in this example is 1:0.3.
The preparation method of the silane modified polyester prepolymer in the embodiment comprises the following steps: (1) Adding low-crystallization polyester polyol into a high-order reaction kettle, heating to 100 ℃, vacuumizing to-0.1 MPa, cooling to 60 ℃, and introducing nitrogen. (2) Adding isocyanate siloxane, and reacting for 3 hours to obtain a silane modified polyester product.
The low crystalline polyester polyol in this example was purchased from PA-56N, a company of Nanjing hand-in-hand chemical technology Co., ltd
The isocyanate siloxane in this example was 3-isocyanatopropyl methyl dimethoxy silane, commercially available from KH-9011, inc. of Jesseca chemical Co., hangzhou.
The preparation method of the single-component moisture-curing adhesive in the embodiment comprises the following steps:
(1) Adding polyester polyol and polyfunctional polyether into a reaction kettle, heating, dehydrating, and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent (accounting for 20% of the weight of the component A), introducing nitrogen to perform prepolymerization reaction, adding a catalyst, and continuing the reaction to obtain a mixture B;
(3) And adding an auxiliary agent and the rest solvent into the mixture B, cooling and discharging to obtain the adhesive.
Example 2
The embodiment 2 of the invention provides an elastic single-component moisture-curing adhesive, which comprises the following raw materials in parts by weight: 80 parts of mixed polyester polyol, 3 parts of polyfunctional polyether, 20 parts of isocyanate, 30 parts of solvent, 0.1 part of catalyst and 7 parts of auxiliary agent.
The mixed polyester polyol in this example comprises 40 parts of semi-crystalline phthalic anhydride-containing polyester polyol, 10 parts of low crystallinity polyester polyol, and 17 parts of high molecular weight polyester polyol.
The semi-crystalline phthalic anhydride-containing polyester polyol in this example is an aromatic dicarboxylic acid or anhydride, and a polycondensate obtained by reacting a diol with a diacid.
Semi-crystalline phthalic anhydride-containing polyester polyols in this implementation were purchased from Su Telin (Nanj) new materials technology Co.Ltd.
The low crystallinity polyester polyol in this embodiment is a polycondensate of an aliphatic dicarboxylic acid and a pendent diol.
The number average molecular weight of the low crystallinity polyester polyol in this example was 2000g/mol.
The low-crystallinity polyester polyol is PA-56N of Nanjing hand-in-hand chemical industry Co., ltd.
The high molecular weight polyester polyol in this example is a polycondensate of diethyl isophthalate, adipic acid, neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol. The high molecular weight polyester polyol in this example is Shandong national chemical Co.
The polyfunctional polyether in this example is a trifunctional polyether, which is purchased from sepiline 3095,095, france.
The isocyanate in this example is a mixture of HDI and IPDI.
In this embodiment, the weight ratio of HDI to IPDI is 1:3.
The solvent in this example was ethyl acetate, a mixture of toluene.
In this example, the weight ratio of ethyl acetate to toluene is 2:1.
The catalyst in this example was bismuth isooctanoate purchased from Jinan Bing chemical Co.
The adjuvant in this example is a silane modified polyester prepolymer which is the reaction product of a low crystalline polyester polyol and an isocyanate siloxane.
The weight ratio of the low crystalline polyester polyol to isocyanate silicone in this example is 1:0.3.
The preparation method of the silane modified polyester prepolymer in the embodiment comprises the following steps: (1) Adding low-crystallization polyester polyol into a high-order reaction kettle, heating to 100 ℃, vacuumizing to-0.1 MPa, cooling to 60 ℃, and introducing nitrogen. (2) Adding isocyanate siloxane, and reacting for 3 hours to obtain a silane modified polyester product.
The low crystalline polyester polyol in this example was purchased from PA-56N, a company of Nanjing hand-in-hand chemical technology Co., ltd
The isocyanate siloxane in this example was 3-isocyanatopropyl methyl dimethoxy silane, commercially available from KH-9011, inc. of Jesseca chemical Co., hangzhou.
The preparation method of the single-component moisture-curing adhesive in the embodiment comprises the following steps:
(1) Adding polyester polyol and polyfunctional polyether into a reaction kettle, heating, dehydrating, and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent (accounting for 20% of the weight of the component A), introducing nitrogen to perform prepolymerization reaction, adding a catalyst, and continuing the reaction to obtain a mixture B;
(3) And adding an auxiliary agent and the rest solvent into the mixture B, cooling and discharging to obtain the adhesive.
Example 3
The embodiment 3 of the invention provides an elastic single-component moisture-curing adhesive, which comprises the following raw materials in parts by weight: 60 parts of mixed polyester polyol, 2 parts of polyfunctional polyether, 10 parts of isocyanate, 15 parts of solvent, 0.05 part of catalyst and 5 parts of auxiliary agent.
The mixed polyester polyol in this example comprises 40 parts of semi-crystalline phthalic anhydride-containing polyester polyol, 10 parts of low crystallinity polyester polyol, and 17 parts of high molecular weight polyester polyol.
The semi-crystalline phthalic anhydride-containing polyester polyol in this example is an aromatic dicarboxylic acid or anhydride, and a polycondensate obtained by reacting a diol with a diacid.
Semi-crystalline phthalic anhydride-containing polyester polyols in this implementation were purchased from Su Telin (Nanj) new materials technology Co.Ltd.
The low crystallinity polyester polyol in this embodiment is a polycondensate of an aliphatic dicarboxylic acid and a pendent diol.
The number average molecular weight of the low crystallinity polyester polyol in this example was 2000g/mol.
The low-crystallinity polyester polyol is PA-56N of Nanjing hand-in-hand chemical industry Co., ltd.
The high molecular weight polyester polyol in this example is a polycondensate of diethyl isophthalate, adipic acid, neopentyl glycol.
The number average molecular weight of the high molecular weight polyester polyol in this embodiment is 4000g/mol. The high molecular weight polyester polyol in this example is Shandong national chemical Co.
The polyfunctional polyether in this example is a trifunctional polyether, which is purchased from sepiline 3095,095, france.
The isocyanate in this example is a mixture of HDI and IPDI.
In this embodiment, the weight ratio of HDI to IPDI is 1:3.
The solvent in this example was ethyl acetate, a mixture of toluene.
In this example, the weight ratio of ethyl acetate to toluene is 2:1.
The catalyst in this example was bismuth isooctanoate purchased from Jinan Bing chemical Co.
The adjuvant in this example is a silane modified polyester prepolymer which is the reaction product of a low crystalline polyester polyol and an isocyanate siloxane.
The weight ratio of the low crystalline polyester polyol to isocyanate silicone in this example is 1:0.3.
The preparation method of the silane modified polyester prepolymer in the embodiment comprises the following steps: (1) Adding low-crystallization polyester polyol into a high-order reaction kettle, heating to 100 ℃, vacuumizing to-0.1 MPa, cooling to 60 ℃, and introducing nitrogen. (2) Adding isocyanate siloxane, and reacting for 3 hours to obtain a silane modified polyester product.
The low crystalline polyester polyol in this example was purchased from PA-56N, a company of Nanjing hand-in-hand chemical technology Co., ltd
The isocyanate siloxane in this example was 3-isocyanatopropyl methyl dimethoxy silane, commercially available from KH-9011, inc. of Jesseca chemical Co., hangzhou.
The preparation method of the single-component moisture-curing adhesive in the embodiment comprises the following steps:
(1) Adding polyester polyol and polyfunctional polyether into a reaction kettle, heating, dehydrating, and vacuumizing to obtain a mixture A;
(2) Cooling the mixture A, adding isocyanate and a solvent (accounting for 20% of the weight of the component A), introducing nitrogen to perform prepolymerization reaction, adding a catalyst, and continuing the reaction to obtain a mixture B;
(3) And adding an auxiliary agent and the rest solvent into the mixture B, cooling and discharging to obtain the adhesive.
Performance test:
(1) Adhesive properties: pouring the prepared adhesive into a trough directly, performing fancy coating on a reflective bead-planting film, drying a solvent through a drying tunnel, compositing reflective materials on a base cloth (hydrophobic cloth, easily heat-shrinkable cloth, elastic cloth and coarse cloth pattern cloth), after solidification, oppositely adhering by using double faced adhesive tape, tearing, and judging that more reflective coating is still reserved on one surface of the base cloth, so that the adhesive is firmly adhered; otherwise, one surface is not reserved with the reflective coating, and the poor bonding fastness is judged.
(2) Washing resistance: pouring the prepared adhesive into a trough filled with ethyl acetate, performing fancy coating on a reflective bead membrane, drying the ethyl acetate through a drying tunnel, compounding reflective materials on base cloth (hydrophobic cloth, heat-shrinkable cloth, elastic cloth and coarse cloth pattern cloth) at the compounding temperature of 50 ℃, rolling after compounding, and stripping after the glue absorbs moisture and is solidified into a membrane to obtain a fancy reflective cloth finished product. The adhesive coating thickness was 30 μm. Adopting a household water washing mode at 60 ℃ of ISO6330, and after washing for 15 times, judging whether the reflective coating falls off, cracks and the like; the reflective coating is almost free from falling off and cracking, and is judged to be better in washing resistance; large-area falling off and poor judgment are carried out; the fabric is free from falling and cracking, and is judged to be inapplicable to elastic fabrics.
Performance test data:
Table 1 shows the results of the adhesion and water wash resistance tests of the one-component moisture-curable adhesives prepared in examples 1 to 3.
TABLE 1
Claims (4)
1. An elastic single-component moisture-curing adhesive is characterized in that, by weight,
The raw materials at least comprise: 60-80 parts of mixed polyester polyol, 2-3 parts of polyfunctional polyether, 10-20 parts of isocyanate, 15-30 parts of solvent, 0.05-0.1 part of catalyst and 5-7 parts of auxiliary agent;
The polyfunctional polyether is trifunctional polyether; the hydroxyl value of the trifunctional polyether is 920-980 mgKOH/g;
the auxiliary agent is silane modified polyester prepolymer which is the reaction product of low-crystallization polyester polyol and isocyanate siloxane;
The mixed polyester polyol comprises 30-50 parts of polyester polyol with the model of PDP-70, 5-20 parts of polyester polyol with the model of PA-56N, 10-30 parts of high molecular weight polyester polyol, and the molecular weight of the high molecular weight polyester polyol is 3900-4100 g/mol.
2. The elastic single-component moisture-curable adhesive according to claim 1, wherein the weight ratio of the polyester polyol with the model number of PDP-70 to the polyester polyol with the model number of PA-56N to the high molecular weight polyester polyol is (35-45): (8-12): (15-20).
3. The elastic single component moisture curable adhesive of claim 1, wherein the catalyst is one or more of bismuth neodecanoate, bismuth laurate, bismuth isooctanoate, bismuth naphthenate, and composite organobismuth zinc.
4. Use of an elastic one-component moisture-curable adhesive according to any one of claims 1 to 3, in reflective material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102816549A (en) * | 2012-07-10 | 2012-12-12 | 华南理工大学 | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof |
| CN105295815A (en) * | 2015-11-11 | 2016-02-03 | 上海康达化工新材料股份有限公司 | Reactive polyurethane hot melt adhesive for reflective fabric and preparation method thereof |
| CN107383353A (en) * | 2017-08-31 | 2017-11-24 | 浙江道明光电科技有限公司 | A kind of preparation method of silane-modified polyester prepolyer |
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| EP3841177A4 (en) * | 2018-08-23 | 2022-04-06 | Henkel AG & Co. KGaA | Moisture curable polyurethane adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816549A (en) * | 2012-07-10 | 2012-12-12 | 华南理工大学 | Silyl-terminated polyether modified polyurethane adhesive, its preparation method and application thereof |
| CN105295815A (en) * | 2015-11-11 | 2016-02-03 | 上海康达化工新材料股份有限公司 | Reactive polyurethane hot melt adhesive for reflective fabric and preparation method thereof |
| CN107383353A (en) * | 2017-08-31 | 2017-11-24 | 浙江道明光电科技有限公司 | A kind of preparation method of silane-modified polyester prepolyer |
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